DE2928744A1 - METHOD FOR PRODUCING NAPHTHALINE SULFOCHLORIDE - Google Patents

Description

I y 4 ö / ^ * ♦

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk

Central area Bg / bc

Patents, trademarks and licenses 1 8 07 TD

Process for the production of naphthalene sulfochloride

The invention relates to a method for producing Naphthalene sulfochlorides by reacting the alkali metal or ammonium salts of the corresponding naphthalene sulfonic acids with thionyl chloride in the presence of catalytically active substances and optionally in the presence of inert solvents or diluents.

It is known that naphthalene sulfochlorides are obtained from the corresponding Sulphonic acids or their alkali metal salts with thionyl chloride in the presence of dialkyl formamides are preferred Dimethylformamide, as a catalyst and optionally in the presence of inert solvents (HeIv. Chim. Acta 42, 1654 <1959)).

Although naphthalene sulfochlorides can be produced in good yields by this process, the use of dimethylformamide has serious disadvantages. It has been found that dimethylformamide and thionyl chloride can give rise to dimethylcarbamoyl chloride (cf. CA. TS ₁ , 48340 m), which has a strong carcinogenic effect in mice (cf. CA. 77, 97540 b).

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It is also known that pyridinium salts of sulfonic acids with thionyl chloride form sulfochlorides in good yields (Synthesis 1974 , 877). According to this reference, the pyridinium salt of the sulfonic acids is first prepared and isolated with excess base and then reacted in crystalline form with thionyl chloride.

However, the process has the disadvantage that the pyridinium salt of the sulfonic acid is first isolated and purified must be and an excess of pyridine is required for the preparation of the pyridinium salt. This will the process is technically complex and less economical -

There has now been a process for making naphthalene sulfochlorides by reacting the alkali metal or ammonium salts of naphthalenesulfonic acids with thionyl chloride found in the presence of catalytically active substances and optionally in the presence of inert solvents or diluents, which is characterized is that you carry out the reaction in the presence of optionally substituted pyridines, tert »aliphatic Amines, secondary amidines and / or quaternary ammonium salts.

Optionally substituted pyridines can be those of the general formula (I)

(I)

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in the ~ 1Γ-

R, R and R_ are identical or different and represent hydrogen, Halogen, a hydroxy, sulfo or Cyano group or an alkyl, aryl, aralkyl, dialkylamino or N-pyridine radical or where

two of the radicals R to R, if they are adjacent are, stand for a benzo radical, can be used in the process according to the invention.

The following halogens may be mentioned: fluorine, chlorine, bromine, iodine, preferably chlorine, bromine.

Examples of possible radicals R ₁ , R ₂ and R ₃ are: alkyl radicals with up to 10 carbon atoms, preferably up to 5 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, tert-butyl, n-pentyl, iso-pentyl, hexyl, octyl, decyl, cyclohexyl, decahydronaphthyl, preferably methyl, ethyl, n-propyl; Aryl radicals with up to 10 carbon atoms, preferably up to 6 carbon atoms, such as phenyl, tolyl, naphthyl, preferably phenyl, tolyl; Aralkyl radicals with up to 14 carbon atoms, preferably up to 8 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenyl butyl, dihydronaphthyl, tetrahydronaphthyl, naphthylmethyl, naphthylethyl, preferably benzyl, phenylethyl;

Dialkylamino radicals with up to 10 carbon atoms, preferably up to to 6 carbon atoms, such as dimethyl, diethyl, dipropyl, dibutyl, diamyl, ethylhexyl, methylcyclohexylamino / Pyrrolidino, piperidino, morpholino, preferably dimethylamino, pyrrolidino, piperidino, morpholino; N-pyridino radicals with up to 12 carbon atoms, preferably up to . to 8 C-atoms like N-Pyridinp, H-Pi cölino., H-Lutidino, N-Collidno, N- (Methyletbylpyridino) "M-Chinolinö," H-Isochinollno, preferably N-pyridino, Εϊ-picolin, -N-iutidino ".

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IHSP.HCTED

Benzo radicals are those with up to 10 carbon atoms, preferably up to 6 carbon atoms, such as benzo, naphtho, prefers benzo.

For example, the following may be mentioned as optionally substituted pyridines: pyridine, picoline, lufidine, collidine, Methylethylpyridine, (N-pyridinio) pyridine chloride, chloropyridine, Cyanopyridine, hydroxypyridine, pyridinesulfonic acid, Dimethylaminopyrxdin, morpholino, pyrrolidino, piperidinopyridine, Quinoline, isoquinoline, preferably pyridine, picoline, lutidine, 4-cyanopyridine, 4-dimethylaminopyrxdine, Isoquinoline.

Addition compounds of optionally substituted pyridine and thionyl chloride can of course also be used can be used in the process according to the invention.

Tertiary aliphatic amines that can be used are those of the general formula (II)

R ₆

NR _Ä (II)

in the

^R 4 ' ^R 5 ^{and R} 6 9 ^are slightly different and for one

Alkyl, cycloalkyl, N-alkenylaldimino, N-alkenylketimino or an N, N-dialky! aminoalkylene radical stand or two respectively. three of the leftovers together one optionally one

or mono-

or bicyclic ring system with up to 10 carbon atoms, preferably up to 8 Carbon atoms, form,

can be used in the process according to the invention.

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- He -

Examples of possible radicals R4 / R5 and R _g are *. Alkyl radicals with up to 6 carbon atoms, preferably up to 3 carbon atoms, such as methyl, ethyl, propyl, η-butyl, isobutyl, tert-butyl, pentyl, hexyl, preferably methyl, ethyl;

Cycloalkyl radicals with up to 10 carbon atoms, preferably up to to 6 carbon atoms, such as cyclopentyl, cyclohexyl, methylcyclohexyl, Cyclooctyl, cyclodecyl, decahydronaphthyl, preferably cyclohexyl;

N-Alkenylaldimino radicals with up to 15 carbon atoms are preferred up to 12 carbon atoms, such as 2-aza-buta-1,3-diene-1,4-diyl, 2-aza-pent-1-en-1,5-diyl, preferably 2-aza-buta-1,3-diene-1,4-diyl;

N-Alkenylketimino radicals with up to 15 carbon atoms, preferably up to ΊΜ. 12 carbon atoms, such as 1-methyl-2-aza-buta-1,3-diene-l ₇ 4-diyl, 1-butyl-2-aza-pent-1-en-1,5-diyl, preferably 1 -Methyl 1-2-aza-buta-1,3-diene-1,4-diyl;

Ν, Ν-dialkylaminoalkylene radicals with up to 9 carbon atoms, preferred up to 4 carbon atoms, such as dimethylaminoethyl, diethylaminoethyl, Dimethylaminopropyl, dimethylaminobutyl, preferably dimethylaminoethyl.

As optionally one or more heteroatoms, such as Oxygen, sulfur or nitrogen containing mono- or bicyclic ring systems are for example: Pyrrolidine, piperidine / morpholine, diazabicyclooctane, Quinuclidine, 4-thiomorpholine, preferably pyrrolidine, Piperidine, morpholine.

For example, tertiary aliphatic amines may be mentioned: Trimethylamine, triethylamine, N-methy! Pyrrolidine,

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-ßr-

N-methyl imorpholine, N-methyl piperidine, tetramethyl ethylenediamine, bis (2-dimethylaminoethyl) methylamine, 1,4-dimethylpiperazine, 1,4-diazabicyclooctane, quinuclidine, 1,4,5,6-tetrahydro-1, 2-dimethylpyrimidine, 1-methylimidazole, 1,2-dimethylimidazole, 1,5-diazabicyclo ^. 3 .Ojnon-5-ene, 1 _r 8-diaza-bicyclo ^ 5.4.O7-undec-7-ene, preferably trimethylamine, triethylamine, N-Methyl-pyrrolidine.

The tert. aliphatic amines can of course also used in the form of their salts such as hydrohalides, sulfates, phosphates in the process according to the invention will.

Quaternary ammonium salts that can be used are those of the general formula (III)

? 4

R ₇ -NR ₅

(III)

in the

R ⁶ and R ^{7 are} identical or different and

for an alkyl, cycloalkyl, N-alkenylaldimino, N-alkenylketimino or an N, N-dialky! Aminoalkylene radical or two or three of the radicals together represent one or more heteroatoms containing mono- or bicyclic ring system with up to 10 carbon atoms, preferably up to 8 carbon atoms, form and

X ^{θ stands} for chloride, bromide, iodide, sulfate, phosphate or hydrogen sulfate,

can be used in the process according to the invention.

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-r-

For example, the following are mentioned as quaternary ammonium salts: tetramethylammonium chloride , tetraethylammonium chloride, NrN-dimethylpyrrolidinium bromide, hexaethylethylenediammonium chloride, preferably tetramethylammonium chloride, tetraethylammonium chloride.

Secondary amidines can be those of the general formula (IV)

R ₈ -NH-CH = NR ₉ (IVJ

in the

Rg and Rg are the same or different and for one Alkyl or cycloalkyl radical or together form a mono- or bicyclic ring system with up to 15 carbon atoms, preferably up to 9 carbon atoms, form,

can be used in the process according to the invention.

Examples of possible radicals R ″ and R ″ are: Alkyl radicals with up to 10 carbon atoms, preferably up to C atoms, such as methyl, ethyl, n-propyl, iso-propyl, -n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, Hexyl, octyl, preferably methyl, ethyl, n-propylj Cyclo-? alkyl radicals with up to 10 carbon atoms, preferably up to 8 carbon atoms, such as cyclohexyl, methylcyclohexyl, cyclooxyl, Cyclodecyl, preferably cyclohexyl.

As mono- or bicyclic ring systems according to the general Formula (IV) may be mentioned: imidazole, hexahydrobenzimidazole, Imidazoline, preferably imidazole.

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For example, the following are mentioned as secondary amidines: N, N'-dimethylformamidine, N-ethyl-N'-cyclohexylformamidine, Imidazole, imidazoline, hexahydrobenzimidazole are preferred Imidazole.

The optionally substituted pyridines, tertiary aliphatic amines, secondary amidines and / or quaternary Ammonium salts can be used in amounts of about 0.5 to about 10% by weight, preferably 2 to 5% by weight, particularly preferably 3 to 4% by weight, based on the alkali metal or ammonium salts of naphthalenesulfonic acid used, can be used in the process according to the invention.

The alkali metal salts of naphthalene sulfonic acids are the lithium, sodium, potassium and / or rubidium salts, preferably the sodium or potassium salt.

As naphthalenesulfonic acids, which are in the form of their alkali metal salts or ammonium salts which can be used in the process according to the invention are, for example: 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,4-, 1,5-, 1,6-, 2,6-, 2,7-naphthalenedisulfonic acid, naphthalene 1 / 3,6-trisulfonic acid, -1,3,5-trisulfonic acid, -1,3,7-trisulfonic acid, preferably 1-naphthalene sulfonic acid, 2-naphthalene sulfonic acid, 1,5-naphthalene disulfonic acid.

In the process according to the invention, the alkali metal or ammonium salts of naphthalenesulfonic acids are generally reacted with about the equivalent amount, preferably with 1.1 to 1.5 molar equivalents, particularly preferably with 1.2 to 1.3 molar equivalents, of thionyl chloride.

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However, it is also possible to implement the naphthalene sulf Carry out onsäuresalze with a larger excess of thionyl chloride, especially if the thionyl chloride the role of the slurrying liquid reaction medium should take.

Then, for example, about 1.5 to about 5 moles, preferably 2 to 3 moles, of thionyl chloride are used per mole of sulfonate. The excess thionyl chloride can be recovered after the end of the reaction and used again in the reaction will.

The reaction according to the invention can also be carried out in the presence Carry out inert solvents or diluents, in which case those given above are approximately equimolar Amounts of thionyl chloride are sufficient.

Particularly suitable solvents or diluents are those compounds which under the reaction conditions are inert and the resulting naphthalene sulfochloride able to solve at least partially.

For example: Aliphatic or aromatic Hydrocarbons with up to 15 carbon atoms, preferably up to 8 carbon atoms, such as hexane, cyclohexane, toluene, xylene, Octane, decalin, cumene, mesitylene, tetralin, preferably toluene and halogenated aliphatic or aromatic Hydrocarbons with up to 15 carbon atoms, preferably up to 8 carbon atoms, such as methylene chloride, chloroform, dichloroethane, Trichlorethylene, tetrachloroethane, 1, 1,2,3,3-pentachloropropane, Hexachlorocyclopentadiene, octachlorocyclopentane, chlorobenzene, di-, trichlorobenzene, chlorotoluene, chloroxylene, preferably chlorobenzene.

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The solvents or diluents can be used individually or as a mixture with one another.

In general, the solvents or diluents are employed in amounts of from about 1/2 to about 5 liters per mole SuIfonat used.

The inventive method can to about 140 ⁰ C, preferably at 50 to 130 ⁰ C at temperatures in the range of from about 20, more preferably at 80 to 100 ⁰ C, are performed.

Although the process according to the invention is preferably carried out at normal pressure, it is also possible to work at elevated pressure (up to about 50 bar).

According to the process according to the invention, the thionyl chloride, presented and the sulfonate added or vice versa Submitted sulfonate and added the thionyl chloride.

The optionally substituted pyridines, tert. aliphatic Anine, secondary amidines and / or quaternary ammonium salts can before, during or after the addition of the second main component be added to the reaction mixture.

If you are working in an inert solvent or diluent, it is advantageous if the alkali metal or ammonium salts of naphthalenesulfonic acids are slurried with the inert solvents or diluents and then the thionyl chloride and the optionally substituted pyridines, tert. aliphatic

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Amines, secondary amidines and / or quaternary ammonium salts adds.

After the reaction has ended, the inert solvent or diluent and / or excess thionyl chloride becomes distilled off, both the inert solvent or diluent and the thionyl chloride again can be used in the reaction.

The remaining crude product can be used as such directly, e.g. for the production of azo dyes, as in the British Patent specification 634 488 or Swiss patent specification 261 840,

can be used or it can if further processing it requires distillation in vacuo or recrystallization with suitable solvents getting cleaned.

The process according to the invention can be carried out either continuously or batchwise.

The yields of naphthalene sulfochlorides achieved by the process according to the invention are high, they are between about 80 and 100% of theory.

It is extremely surprising that the process of the invention results in a smooth reaction gives such good yields of naphthalenesulfonic acids. From HeIv. Chim. Acta 42., 1654 (1959) is namely known that the reaction with thionyl chloride in the presence of pyridine as a catalyst is limited to carboxylic acids is.

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The following examples are intended to illustrate the invention Illustrate procedures without, however, restricting them to these examples.

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example 1

104 g of sodium naphthalenesulfonate-2 are slowly added to a mixture of 100 ml of thionyl chloride and 3.0 g of pyridine, which was heated in an oil bath at 40 ⁰ C.

At an oil bath temperature of 100 ⁰ C for 1.5 hours under reflux is then heated to boiling until the gas evolution stopped and then stirred for a further 2 hours.

Excess thionyl chloride is distilled off. Man receives 130.3 g of crude product, the 78.6% 2-naphthalene sulf ochloride contains (aniline titration), this corresponds to a 99.9% yield, i.e. quantitative yield within the range the analytical error limits.

More examples with appropriate experimental Implementation is given in the form of a table.

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Tabel

Ex. Use Kata crowd £ 3 weight percent Yield to Sodium-2- lyser Pyridine 3 Naphthalene- naphthalene- 4-picoline 3 2-sulfochlo- sulfpnate 4-cyano- 3 rid / ÜolJ pyridine 7th C * J 2 2.3 2-picoline 3 100 3 0.46 4- (N, N-Di- 3 98.7 4th 0.46 methyl-ami- 100 no) pyridine 5 0.47 Isoquinoline 6 91.3 6th 0.46 Trimethyl- 3 99.6 amine (as Hydrochloric 7th 0.50 rid) 1OO 8th 0.46 Triethyl 3 93.5 amine N-methyl-3 pyrrolidine 9 0.47 Imidazole 3 93.3 Tetraethyl 3 10 0.46 ammonium- 100 chloride 11 0.46 Pyridine 2 96.9 12th 0.46 Pyridine 4 82.0 Pyridine 10 13th 0.46 89.6 14th 0.46 99.3 15th 0.46 1OO

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Example 16

1 mol of sodium 2-naphthalenesulfonate and 7.0 g of pyridine are suspended in 600 ml of chlorobenzene and heated to 40.degree. With stirring is added dropwise 143 g (1.2 mol) of thionyl chloride, heated for 6 hours at 10O ⁰ C and distilled chlorobenzene and remaining thionyl chloride off in vacuo.

The yield of naphthalene sulfochloride is 99%. Example 17

115.1 grams (0.5 moles) of sodium 1-naphthalenesulfonate are used implemented as in Example 1; however, 6.0 g of pyridine are added and stirs for a total of 3 hours. The yield was 146.4 g of crude product, the 76.8% of naphthalene-1-sulfochloride (99.1% yield).

Example 18

116.0 g (0.5 mol) of purified naphthalene-1,5-disulfonic acid disodium salt, 6 g of pyridine and 300 g of SOCl ₂ were reacted with one another as in Example 1. Naphthalene-1,5-disulfochloride was obtained, which still contained approx. 28% sodium chloride. The yield by the aniline titration method was 90%.

Example 19

The procedure described in Example 14 is used however, the potassium salt of naphthalene-2-sulfonic acid. the The yield was quantitative.

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Claims (10)

REQUIRED patent claims 1)! Process for the production of Naphthalenesulfochlo ™ ^ - ^ riden by reacting the alkali metal or ammonium salts the naphthalenesulfonic acids with thionyl chloride in the presence of catalytically active Substances and optionally in the presence of inert solvents or diluents, characterized in that the reaction is carried out in the presence of optionally substituted pyridines, tert. TO aliphatic amines, secondary amidines and / or quaternary ammonium salts. 2) Method according to claim 1, characterized in that that optionally substituted pyridines are those of the general formula (i) (D sets in,
in the ^R l ' ^R 2 ^{and R} 3 9 are ^leic or different and represent hydrogen, halogen, a hydroxy, sulfo or cyano group or an alkyl, aryl, aralkyl, dialkylamino or N-pyridine radical, or where two of the radicals R ₁ to R, when they are adjacent, represent a benzo radical. 3) Method according to claims 1 and 2, characterized thereby-5 draws that pyridine, picoline, lutidine, 4-dimethylaminopyridine, 4-cyanopyridine, isoquinoline begins. Le A 19 725 030066 / 0U3 --17- 4) Method according to claim 1, characterized in that that the tertiary aliphatic amines are those of the general formula (II) sets in,
in the
R4 / R5 and R, NR ₄
^R 5 (II) are identical or different and represent an alkyl, cycloalkyl, N-alkenylaldimino, N-alkenylketimino or an N, N-dialky! Aminoalkylene radical or two or three of the radicals together contain one optionally containing one or more heteroatanes Form mono- or bicyclic ring system with up to 10 carbon atoms 5) Process according to Claims 1 and 4, characterized in that one is trimethylamine, triethylamine, N-methyl! Pyrrolidine begins. 6) Method according to claim 1, characterized in that that the quaternary ammonium salts are those of the general formula (III) (III) Le A 19 725 030066 / 0U3 - te- - starts, —ο> in the R ⁴ , R ⁵ , R and R are identical or different and represent an alkyl, cycloalkyl, N-alkenylaldimino, N-alkenylketimino or a Ν, Ν-dialkylaminoalkylene radical, or two or three of the radicals together are optionally one or more Mono- or bicyclic ring system containing heteroatoms with up to 10 carbon atoms, preferably up to 8 carbon atoms, and X ^{θ stands} for chloride, bromide, iodide, sulfate, phosphate or hydrogen sulfate. 7) Method according to claims 1 and 6, characterized in that that one uses tetramethylammonium chloride, tetraethylammonium chloride. 8) Method according to claim 1, characterized in that that the secondary amidines are those of the general formula (IV) R ₈ -NH-CH = NR ₉ (IV sets in,
in the Rg and Rg are the same or different and for one Alkyl or cycloalkyl radical or together form a mono- or bicyclic ring system with up to 15 carbon atoms. 9) Method according to claims 1 and 8, characterized in that that imidazole is used. Le A 19 725 030066 / 0U3 10) Process according to Claims 1 to 9, characterized in that the optionally substituted Pyridines, tert. aliphatic amines, secondary amidines and / or quaternary ammonium salts in quantities from 0.5 to 10% by weight, based on the alkali metal or ammonium salts of the naphthalenesulfonic acids used, begins. Le A 19 725 030066/0143